Photosensitive material for electrophotography including indoline derivatives

ABSTRACT

1. A COMPOUND OF THE FORMULA   1-(R2-(CH2)M-),2,2-(3-R-2-ISOXAZOLIN-5,5-YLIDENE&lt;),3,3-   DI(H3C-),R1-INDOLINE   WHEREIN R1 IS HYDROGEN ATOM, HALOGEN ATOM, ALKYL HAVING 1 TO 4 CARBON ATOMS, ALKOXY HAVING 1 TO 4 CARBON ATOMS, ALKOXYCARBONYL HAVING ALKYL HAVING 1 TO 4 CARBON ATOMS, NITRO, R2 IS HYDROGEN ATOM, HYDROXYL, ALKOXYCARBONYL HAVING ALKYL HAVING 1 TO 4 CARBON ATOMS, CYAN OR PHENYL, R IS SUBSTITUTED PHENYL (WHERE THE SUBSTITUENT IS HYDROGEN ATOM, HALOGEN ATOM, ALKYL HAVING 1 TO 4 CARBON ATOMS, OR ALKOXY HAVING 1 TO 4 CARBON ATOMS), M IS AN INTEGER FROM 1 TO 4.

United States Patent O 3,850,949 PHOTOSENSITIVE MATERIAL FOR ELECTRO-PHOTOGRAPHY INCLUDING INDOLINE DERIVATIVES Hisatake Ono, Syu Watarai,and Harumi Katsuyama, Asaka, Japan, assignors to Fuji Photo Film $0.,LttL, Kanagawa, Japan No Drawing. Filed Oct. 6, 1971, Ser. No. 187,190Claims priority, application Japan, Oct. 6, 1970, 87,788 Int. Cl. C07d85/16 US. Cl. 260-307 F 4 Claims ABSTRACT OF THE DISCLOSURE An organicphotoconductive material for electrophotography consisting essentiallyof indoline derivatives represented by the following general formula (A)wherein R is hydrogen atom, halogen atom, alkyl group having 1 to 4carbon atoms, alkoxy group having 1 to 4 carbon atoms, alkoxycarbonylgroup having alkyl group having 1 to 4 carbon atoms, nitro group, oralkylene chain having 1 to 3 carbon atoms, R is hydrogen atom, hydroxylgroup, alltoxycarbonyl group having alkyl group having 1 to 4 carbonatoms, cyan or phenyl group, R is substituted phenyl group (wheresubstituted group is hydrogen atom, halogen atom, alkyl group having 1to 4 carbon atoms, or alkoxy group having 1 to 4 carbon atoms), alkylenechain having 1 to 3 carbon atoms or phenylene group, In is an integer 1to 4.

This invention relates to an organic photoconductive material forelectrophotography. As photoconductive materials applicable toelectrophotography there are known inorganic substances such as seleniumand zinc oxide, organic lower molecular compounds such as anthracene,chrysene and benzidine, and higher molecular compounds such aspoly-N-vinylcarbazole, polyvinylnaphthalene and polyvinylanthracene.

This invention relates to an organic photoconductive material having anovel structure completely different from known materials, and providesa photosensitive material having as an essential componentZ-substitutedmethylene-indoline derivatives represented by the followinggeneral formula (A):

ca ca 3 CH2C-R (A) R1 v H o-u wherein R is hydrogen atom, halogen atom,alkyl group having 1 to 4 carbon atoms, alkoxyl group having 1 to 4carbon atoms, alkoxycarbonyl group having alkyl group having 1 to 4carbon atoms, nitro group, or methylene chain having 1 to 3 carbonatoms, R is hydrogen atom, hydroxyl group, alkoxycarbonyl group havingalkyl group having 1 to 4 carbon atoms, cyan or phenyl group, R issubstituted phenyl group (wherein substituted group is hydrogen atom,halogen atom, alkyl group having 1 to 4 carbon atoms or alkoxyl grouphaving 1 to 4 carbon atoms), methylene chain having 1 to 3 carbon atomsor phenylene group, m is an integer from 1 to 4.

The above formula (A) is represented by the following formulae (I) to(IV).

(H CH3 CH3 wherein R is hydrogen atom, halogen atom, alkyl group having1 to 4 carbon atoms, alkoxyl group having 1 to 4 carbon atoms,'alkoxycarbonyl group having alkyl group having 1 to 4 carbon atoms ornitro group, R is hydrogen atom, hydroxyl group, alkoxycarbonyl grouphaving alkyl group having 1 to 4 carbon atoms, cyan or phenyl group, Ris hydrogen atom, halogen atom, alkyl group having 1 to 4 carbon atoms,or alkoXyl group having 1 to 4 carbon atoms, R, is direct bond of carbonatoms, methylene chain having 1 to 3 carbon atoms or phenylene group, Inis an integer from 1 to 4, n is zero, an integer 1 or an integer 2, x isdegree of polymerization.

Compounds represented by the above formulae are novel compounds preparedby addition reactions of Z-methylene-indoline derivatives with nitrileoxides. Nitrile oxides are active intermediates produced by reactinghydroxam ic acid halides with bases and provide ring compounds by1,3-dipolar cyclo add'ition to multiple bonds such as acetylene,nitrile, carbonyl, olefin and the like. Mechanism of these reactions isknown as dipole ring formation reaction, and concerning it R. Huisgenwrote genera-l considerations in Angewandte Chemie, 75, 604 (1963).Recently synthesis of polymers containing heterocycles uti- 'lizing the1,3-dipolar cycloaddition reaction were re ported, for instance, seeIwakura, Shirais'hi et al. Bulletin of the Chemical Society of Japan,38, 335 (1965); ibid., 38, 513 (1965); and Polymer Letters, 4, 305(1966) etc.

With reference to these reports, many addition prod- 'ucts were obtainedby reacting various 2-methyleneindolines with various hydroxamic acidhalides in the presence of a base. It was proved that the structure ofthese addition products is a spiro (indol=ine-2,5'-isoxazoline)structure from the results of elemental analysis and measurements ofinfrared absorption spectrum, ultraviolet absorption spectrum, visiblemay absorption spectrum, NMR spectrum, etc. For instance1,3,3-trimethyl-2-methylene- 5-chloroindoline and benzhydroxamic acidchloride were dissolved in ether. To the solution was added dropwise, 1Nsodium hydroxide solution and the mixture was stirred at roomtemperature for 30 minutes. Then the ether layer was dried andconcentrated, in reduced pressure and crystals were obtained.

Thus isolated compound was colorless, needle-like and had a meltingpoint of 167 to 168 C. and had the following results of elementalanalysis: carbon 69.49%, hydrogen 5.86%, nitrogen 8.36%. The result-swere in good agreement with theoretical value of 1,3,3-trimethyl-5-chloro-3'-phenyl-spiro (indoline-2,5'-isoxazoline) carbon 69.59%,hydrogen 5.86%, nitrogen 8.57%. Meanwhile, the agreement was supportedby the fact that the parent peak (M+) of mass spectrum was 326, and thecompound had the absorption in infrared absorption spectrum at 1560 cm."which agreed with 11C=N, and had a maximum absorption in ultravioletabsorption absorptions it was concluded that the compound had anindoline type structure altered from the methylene-indoline typestructure starting material. Moreover, in NMR spectrum(tetramethylsilane dissolved in deuterated chloroform solution, internalreference) the compound had peaks at 6 value (as ppm.) 1.25 (S, 3H),1.34 (8, 3H), 2.61 (S, 3H), 3.03, 3.33, 3.38, 3.39 (AB type 2H ]J|=l8.0cps.) and ring protons (8H) were observed.

On the basis of above-mentioned data it is obvious that the compound ofthis invention has spiro (indoline-2,5- isoxazoline) structure.

Meanwhile, a high polymer compound obtained by the reaction of 5,5-methylenebis- 1,3 ,3-trimethyl-2-methylene-indoline) withdichloroglyoxime had a maximum absor-ption in ultraviolet absorptionspectrum at 262 m and in NMR spectrum the high molecular compound hadpeaks at 5 value 1.24 (S), 137 (S), 2.66 (S), 3.01, 3.34, 3.67(Transition type to A type from AB type) and multiplate ring protons(8H). The intensity ratio of these peaks was 6:6:4:2:6, and infraredabsorption spectrum also agreed nearly with spectrum of the abovementioned mono-spiro-compound. From these data it is obvious that thehigh molecular compound of this invention has a structure containingspiro-(indoline 2,5 isoxazoline) as repetition unit.

In this invention, it was found that the many compounds which wereprepared and which had structures which were confirmed as stated aboveare useful as organic photoconductive materials for electrophotography.These compounds are listed in Table 1 to Table 4.

The high molecular compounds of this invention are soluble in var-ionsorganic solvents such as chloroform, tetrahydrofuran,N,N-dimethyltormamide, N,N-dirnethylacetamide, N-methyl-Z-pyrrolidoneand the like, and are so highly polymerized that they give a strong filmby applying a solution of the polymer in a lower boiling solvent such astetrahydrofuran to a metallic plate and drying, and their reducedviscosity value (u e) was spectrum at 262 mu (e=2.58 10 On the basis ofthese about from 0 3 to TABLE 1 CH3 CH3 Ra 4 H ON CH:

Com ound CHCla numlger R1 Ra M.P. C.) )tmax. (M /J1 (e) H 118 260 (1.X1O -H 167-168 262 (2. 53x10 Cl -171 268 (2 18x10 H 123-124 304 (3 07 10-C1 184485 265 (2. 16x10 372 (2. 04X10 -H 210. 5-211. 5 260 (1. 83X10373 (2. 13x10) -H 155 259 (1. 94x10 -CH3 140 260 (2. 05X10 TABLE 2 CH3CH CH3 CH Rt CHg- OR4- OCHQ R1 ON N-0 N/ I I CH3 C 3 Compound M.P. CHCI;number R1 R4 A max. 101

-H Direct bond of carbon atoms 231 259 (3 06x10 Cl .(10 154; 262 (406x10 CzH5OCO- do 242 305 (4 64x10 -H -CHz 200 259 (3 30x10 13 H (CH2)3259 (3 21x10 14.....I H 273 299 (3. 30x10 TABLE 3 CH3 CH3 CH3 CH3 R3 (9(cm)n K Q Ra N-O I ON (C|H1)m ((iJHDm Compound number n m R2 R3 M.P. C.)A u (6) 0 2 --COOCzH --H 210 265 (5.78Xl04) 1 1 -H 'H 196 264 (4.32X104)1 1 H P-Cl- 250 274 (3.97X104) TABLE 4 CH CH CH3 CH CH1- ii-R4-H-CH; N/ON \N H2)m 0m R2 R: x

c d R ti i MP ompoun sec on per- ,sol eut number n m R; R. time (hr.)cent 0. V

19 0 1 H Direct bond of carbon atoms.. 1 80 273-275 0.15 (THF). 20 1 1-H do 20/60 90 300 0.49(THF). 1 1 H 3 90 230-240 0.11(THF). 1 2 20/60 70174-185 0.06(THF).

1 1 1 90 300 0.27(NMP).

24 0 1 20/60 (1) 300 Impossible to measure;

25 1 1 1 80 300 0.15(NMP).

0 3 CN Direct bond ofearbon atoms 1 90 300 0.11(THF). 2 2 -OH .d0 1250-270 0.07(THF).

1 Quantitative.

For utilizing lower molecular compounds which were above-mentioned foruse as materials for electrophotography, coatings as light-sensitivelayer are made by dissolving the compounds in organic solvents withhighly insulating coating-forming resinous binders, applying thesolutions to comparatively electroconductive supports and drying, ifdesired. It is also possible to add plasticizers and sensitizers therebyto improve the characters of coatings and to increase greatly thesensitivity. In the case of high molecular compounds listed in Table 4,coatings for use as a light-sensitive layer are made by dissolving thehigh molecular compounds in organic solvents without highly insulatingcoating-forming resinous binder, applying the solution to comparativelyelectroconductive supports and drying, if desired. It is also possibleto add plasticizers and sensitizers thereby to improve thecharacteristics of the coatings and to increase greatly the sensitivity.

As coating-forming resinous binders, styrene-butadiene copolymers,polystyrenes, chlorinated rubbers, polyvinyl chlorides, vinylchloride/vinyl acetate copolymers, polyvinylidene chloride,nitrocelluloses, polyvinyl acetates, polyvinylacetals, polyvinyl ethers,silicon resins, methacrylic resins, acrylic resins, phenol resins, alkydresins, urea/aldehyde resins, etc. may be used, and as electroconductivesupports, metallic plates, electroconductive papers, electroconductiveplastic films, etc. may be used, and as plasticizers chlorinatedbiphenyls, chlorinated paraflins, phosphate plasticizers, phthalateplasticizers, etc. may be used, and as sensitizers, conventionalsensitizers such as tetracyanoethylene, tetracyanoquinodimethane,

chloranil, naphthoquinone, anthraquinone, Methylene Blucei, CrystalViolet and Malachite Green, etc. may be use It is preferred to suitablycombine these materials and apply them on an electroconductive supportto provide a dried coat of 2 to 20 microns in thickness. Whenorganophotoconductive component is more than 25 percent of the totalcomponents of the coating, electrophotographically excellentcharacteristics are obtained.

The light-sensitive layer obtained by above-mentioned process isuniformly charged by corona discharge according to the conventionalmethod of electrophotography, and after image-exposure is developed bycascade development, liquid development, etc. In the case of cascadedevelopment it may be fixed by weakly heating after development or bystanding in solvent-vapor capable of dissolving the resin of toner.

This invention is further illustrated by the following examples.However, this invention shall not be limited to the following examples.

EXAMPLE 1 Half a gram of compound No. 1 in Table 1 and 20 ml. of 10%polystyrene solution in tetrahydrofuran were blended uniformly, theresulting solution was applied to an aluminum plate support to provide adried coating of 0.5 micron in thickness.

After drying it was charged with positive electricity in a dark place,and a positive picture film was placed upon it, then they were exposedwith a high-pressure 7 mercury lamp (Toshiba, SHL-100) from 30 cm. inheight for about seconds. Then it was developed with toner charged withnegative electricity (for instance developer for Xerox 914), whereby apositive picture was developed, and allowed to stand in an atmosphere oftrichloroethylene for fixation, whereby a clear positive image wasobtained.

EXAMPLE 2 Compound No. 2 in Table 1 was applied and dried as describedin Example 1. After exposure for 2 seconds similar treatments wererepeated and a clear positive image was obtained.

EXAMPLE 3 By treating compound No. 9 in the exactly similar manner ofExample 1 a clear positive image was obtained.

EXAMPLE 4 Compounds No. in Table 3 was applied and dried as described inExample 1. After exposure for about 1 second similar treatments wererepeated and a clear positive image was obtained.

EXAMPLE 5 Half a gram of compound No. 21 in Table 4 was dissolved in 3ml. of tetrahydrofuran, then the solution was applied to an aluminumplate to provide a dried coating of 5 microns in thickness. This testplate was exposed for about 1 second as described in Example, and bytreating as in Example 1 a clear positive image was obtained.

EXAMPLE 6 A similar test plate as in Example 5 was charged with positiveelectricity in a dark place, and a positive image film was placed uponit; then they were exposed with 100 W. tungsten lamp (Toshiba lamp) from30 cm. in height and then by treating as described in Example 1 a clearpositive image was obtained.

EXAMPLE 7 Half a gram of Compound 23 in Table 4 was dissolved in 4 ml.of tetrahydrofuran. After separation of a small amount of insolublesubstances, the solution was applied as described in Example 5 and thetest plate was exposed for about 3 seconds as in Example 6. Furthertreatments as described in Example 1 gave a clear image.

EXAMPLE 8 A test plate of Example 7 was charged with electricity in adark place and overlaid with a positive image film, then they wereexposed with a diazotype duplicator (for instance Recopy-standard) atfull reproduction speed (for instance in the case of Recopy-standard,the dial was set at 'Recopy-standard is a diazo-type wet copying machineequipped with a mercury lamp and manufactured by Ricoh Kabushiki Kaisha,Japan. Further treatments as described in Example 1 gave a clear image.

EXAMPLE 9 To the solution of Example 7 was added 0.001 g. of chloranil,and similarly in Example 7 the solution was ap plied and the test platewas exposed, developed and fixed. When the exposure time was less thaneven 1 second, a clear image was obtained.

What is claimed is:

1. A compound of the formula wherein R is hydrogen atom, halogen atom,alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms,

8. alkoxycarbonyl having alkyl having 1 to 4 carbon atoms, nitro, R ishydrogen atom, hydroxyl, alkoxycarbonyl having alkyl having 1 to 4carbon atoms, cyan or phenyl, R is substitutedphenyl (where thesubstituent is hydrogen atom, halogen atom, alkyl having 1 to 4 carbonatoms, or alkoxy having 1 to 4 carbon atoms), m is an integer from 1 to4.

2. A compound of the formula CH CH3 wherein R is hydrogen atom, halogenatom, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbonatoms, alkoxycarbonyl having alkyl having 1 to 4 carbon atoms or nitro,R is hydrogen atom, hydroxyl, alkoxycarbonyl having alkyl having 1 to 4carbon atoms, cyan or phenyl, R is hydrogen atom, halogen atom, alkylhaving 1 to 4 carbon atoms, or alkoxy having 1 to 4 carbon atoms, m isan integer from 1 to 4.

wherein R is hydrogen atom, hydroxyl, alkoxycarbonyl having alkyl having1 to 4 carbon atoms, cyan or phenyl, R is hydrogen atom, halogen atom,alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms, mis an integer from 1 to 4, n is zero, an integer 1 or an integer 2.

4. A compound of the formula CH, CH; CH; on,

\/cHg- |C-R4 Eli-CH2 R1 R1 0N N-O wherein R is hydrogen atom, halogenatom, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbonatoms, alkoxycarbonyl having alkyl having 1 to 4 carbon atoms or nitro,R is hydrogen atom, hydroxyl, alkoxycarbonyl having alkyl having 1 to 4carbon atoms, cyan or phenyl, R is direct bond of carbon atoms, alkylenechain having 1 to 3 carbon atoms or phenylene, and m is an integer from1 to 4. References Cited UNITED STATES PATENTS 3,429,892 2/ 1969 Loev260-307 RAYMOND V. RUSH, Primary Examiner US. Cl. X.R. 961.5, 1.6

1. A COMPOUND OF THE FORMULA